EP0476256A1 - Process for controlling granulation in the preparation of expandable styrene polymers by suspension polymerization - Google Patents
Process for controlling granulation in the preparation of expandable styrene polymers by suspension polymerization Download PDFInfo
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- EP0476256A1 EP0476256A1 EP91111717A EP91111717A EP0476256A1 EP 0476256 A1 EP0476256 A1 EP 0476256A1 EP 91111717 A EP91111717 A EP 91111717A EP 91111717 A EP91111717 A EP 91111717A EP 0476256 A1 EP0476256 A1 EP 0476256A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
Definitions
- expandable polystyrene by an aqueous suspension polymerization produces a relatively wide range of particles. About 90% of the particles are in the range between 0.5 and 2.0 mm with a maximum between 0.7 and 1.0 mm.
- Fine material is processed in the packaging sector, while coarse material is primarily used in the construction sector (insulation, impact sound insulation).
- the reason for the occurrence of instabilities and the poor reproducibility should be found among other things in the characteristics of the particle size development during the suspension polymerization.
- the initially very fine particles grow only insignificantly in the first 120 minutes of polymerization. After that, there is a drastic particle growth within a short time (120 to 180 min) until the desired final grain size is reached at the setting point. At the point of settling, the styrene conversion is approximately 70%. At this point, the viscosity of the particles is so high that coalescence processes and particle formation by fragmentation practically no longer take place. That means the particles keep their identity.
- Seed polymerization is an alternative.
- a fully polymerized grain of a defined size is introduced and a certain amount of organic phase is metered in (EP-PS 102 655; US-PS 154 184; FR-OS 2 238 717; FR-OS 2 238 718; DE-OS 2 338 133) .
- This method enables the grain size of the polymerization to be influenced via the metered amount.
- Seed polymerization requires the presence of a seed grain free of coating agent. Its manufacture requires its own polymerization process and thus reduces the space / time yield. The homogeneous distribution of the replenished organic phase requires a very slow metering rate. Otherwise there is an undesirable formation of new particles (fines).
- the object of this invention was to find a process for controlling the grain size of the suspension polymerization which can be driven stably in the critical area and with which a coarse final grain size can be achieved.
- a new particle formation is undesirable because it leads to an increase in the fine fraction.
- the metering rate should therefore be chosen so that there are as far as possible no free styrene droplets in the suspension.
- Another criterion determining the dosing speed is the point of settling of the particles.
- the residual styrene content should always be ⁇ 30% by weight. In this way, the particles retain their identity and the suspension cannot become unstable.
- the suspension polymerization is continued in a conventional manner.
- the normal polymerization cycle is practically interrupted only for the period of metering.
- the associated cycle time extension is largely due to the increase in the phase ratio org / aq. Phase and thus the yield is compensated.
- the dosing in the documents cited above does not take place at a specific dosing rate that keeps the residual styrene content constant and therefore makes controlled grain control impossible.
- the metering rate should be chosen such that the residual monomer content is always less than or equal to 30% by weight.
- the batch is polymerized out.
- a 2-hour dosing of 20% by weight of organic phase after a reaction time of 180 minutes proved to be optimal with regard to the target size of grain coarsening.
- styrene or monomer mixtures with at least 50 percent by weight of styrene are used as the monomer.
- Suitable comonomers are e.g. B. ⁇ -methyl styrene, halogenated styrenes, acrylonitrile, esters of acrylic and methacrylic acid of alcohols with 1 to 8 carbon atoms, N-vinyl compounds, such as N-vinyl carbazole.
- the suspension polymerization is carried out at temperatures from 80 to 130 ° C. It is initiated in the usual way with one or more radical-forming substances, examples being t-butyl benzoate, t-butyl peroctoate, di-t-butyl peroxide, dibenzoyl peroxide or mixtures thereof.
- organic protective colloids such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl pyrrolidone copolymers and hydroxyalkyl celluloses or mineral suspension aids such as finely divided tricalium phosphate and barium phosphate or else mixtures of organic protective colloids and mineral suspending agents can be used as suspension stabilizers.
- the blowing agent for the polymer beads can be added either during or after the polymerization, depending on the process. It is not possible to add propellant before the end of the dosing.
- blowing agents liquid hydrocarbons, such as pentane, hexane, cycloaliphatic hydrocarbons, such as cyclohexane or halogenated hydrocarbons, such as dichlorodifluoromethane, 1,2,2-trifluoro-1,1,2-trichloroethane or else mixtures of these compounds.
- the amount of blowing agent is 3 to 15 wt .-%, preferably between 5 and 8 wt .-% based on the styrene polymer.
- the expandable styrene polymers can contain the usual flame retardants such as organic halogen compounds, especially bromine compounds; the fully or partially brominated oligomers of butadiene or isoprene with an average degree of polymerization of 2 to 20, e.g. B. 1,2,5,6-tetrabromocyclooctane, 1,2,5,6,9,10-hexabromocyclodecane, brominated polybutadiene with a degree of polymerization of e.g. B. 3 to 15.
- organic halogen compounds especially bromine compounds
- bromine compounds especially bromine compounds
- the organic halogen compounds are present in the expandable styrene polymer in amounts of 0.4 to 3% by weight.
- the known synergists can be used in customary amounts, preferably organic peroxides, especially those with a half-life of at least two hours at 373 K.
- the halogen compounds can also be used in a known manner in amounts of 0.05 to 1% by weight to improve the minimum residence time be used.
- the expandable styrene polymers can also contain additives such as dyes, fillers and stabilizers. After production they are in pearl form and have a particle diameter between 0.5 and 2.0 mm.
- the styrene polymers are foamed further in the pre-expanded state by heating in molds which do not close in a gas-tight manner and sintered to form foam bodies which correspond in their dimensions to the internal cavity of the molds used.
- the mixture is heated to 90 ° C. with stirring and kept at this temperature for 3 h.
- a further 10.2 kg of styrene, which contain 40.8 g of benzoyl peroxide and 25.5 g of tertiary butyl perbenzoate, are then metered in within 2 hours. After metering is complete, the mixture is stabilized with 25.5 g of polyvinyl alcohol.
Abstract
Description
Bei der Herstellung von expandierbarem Polystyrol durch eine wäßrige Suspensionspolymerisation fällt ein relativ breites Kornspektrum an. Etwa 90 % der Teilchen liegen im Bereich zwischen 0,5 und 2,0 mm mit einem Maximum zwischen 0,7 und 1,0 mm.The production of expandable polystyrene by an aqueous suspension polymerization produces a relatively wide range of particles. About 90% of the particles are in the range between 0.5 and 2.0 mm with a maximum between 0.7 and 1.0 mm.
Unterschiedliche Kornfraktionen gehen in verschiedene Anwendungsgebiete. So wird feines Material im Verpackungssektor verarbeitet, während grobes Material in erster Linie im Bausektor (Isolierung, Trittschalldämmung) Verwendung findet.Different grain fractions go into different areas of application. Fine material is processed in the packaging sector, while coarse material is primarily used in the construction sector (insulation, impact sound insulation).
Die Marktanforderungen wechseln dabei ständig. Daher ist es wünschenswert, die Körnungsverteilung während der Polymerisation gezielt zu steuern, ohne die Suspensionsstabilität zu gefährden. Die bisher einzige Möglichkeit der Steuerung besteht in einer qualitativen und quantitativen Variation der Suspensionsmittelzusammensetzung (DE-OS 33 15 69, DE-OS 33 15 70, JA 945 248, DE-OS 37 28 044).The market requirements are constantly changing. It is therefore desirable to control the particle size distribution during the polymerization without endangering the suspension stability. The only control option so far has been a qualitative and quantitative variation of the suspension composition (DE-OS 33 15 69, DE-OS 33 15 70, JA 945 248, DE-OS 37 28 044).
Eine gezielte Beeinflussung der Körnungsverteilung ist bei diesen Verfahren während der Suspensionspolymerisation nicht mehr möglich, lediglich für den nächstfolgenden Ansatz kann die Suspensionsmittelmenge neu festgelegt werden.In these processes, it is no longer possible to influence the particle size distribution in a targeted manner, only the amount of suspension medium can be redefined for the next batch.
Die gezielte Einstellung grober Körnungen führt dabei im kritischen Polymerisationsbereich (120 bis 180 min) immer wieder zu Instabilitäten, denen durch eine vorzeitige Nachstabilisierung begegnet wird. Das hat jedoch in der Regel erhöhte Innenwassergehalte und ein sehr breites Kornspektrum (viel Feingut) zur Folge.The targeted setting of coarse grains repeatedly leads to instabilities in the critical polymerization range (120 to 180 min), which are countered by premature post-stabilization. However, this usually results in increased internal water contents and a very wide grain spectrum (lots of fine material).
Die Ursache für das Auftreten von Instabilitäten und die schlechte Reproduzierbarkeit dürfte unter anderem in der Charakteristik der Teilchengrößenentwicklung während der Suspensionspolymerisation zu suchen sein. Die zunächst sehr feinen Teilchen wachsen in den ersten 120 min Polymerisationszeit nur unwesentlich. Danach kommt es innerhalb kurzer Zeit (120 bis 180 min) zu einem drastischen Teilchenwachstum bis zum Erreichen der gewünschten Endkörnung am Absetzpunkt. Am Absetzpunkt beträgt der Styrolumsatz ca. 70%. Die Viskosität der Teilchen ist zu diesem Zeitpunkt so hoch, daß Koaleszenzvorgänge und Teilchenneubildung durch Zerteilung praktisch nicht mehr stattfinden. Das heißt, die Teilchen behalten ihre Identität.The reason for the occurrence of instabilities and the poor reproducibility should be found among other things in the characteristics of the particle size development during the suspension polymerization. The initially very fine particles grow only insignificantly in the first 120 minutes of polymerization. After that, there is a drastic particle growth within a short time (120 to 180 min) until the desired final grain size is reached at the setting point. At the point of settling, the styrene conversion is approximately 70%. At this point, the viscosity of the particles is so high that coalescence processes and particle formation by fragmentation practically no longer take place. That means the particles keep their identity.
Unmittelbar vor dem Absetzpunkt ist die Suspension relativ instabil und die Tendenz zum Aufrahmen wird mit abnehmender Suspensionsmittelmenge immer größer. Außerdem bedingt dieser Verlauf der Teilchengrößenentwicklung eine schlechte Reproduzierbarkeit der Ansätze.Immediately before the point of settling, the suspension is relatively unstable and the tendency towards creaming increases as the amount of suspension medium decreases. In addition, this course of particle size development leads to poor reproducibility of the batches.
Als Alternative bietet sich die Saatpolymerisation an. Dabei wird ein vollständig auspolymerisiertes Korn definierter Größe vorgelegt und eine bestimmte Menge organischer Phase nachdosiert (EP-PS 102 655; US-PS 154 184; FR-OS 2 238 717; FR-OS 2 238 718; DE-OS 2 338 133). Dieses Verfahren ermöglicht über die Dosiermenge eine Beeinflussung der Körnung der Polymerisation.Seed polymerization is an alternative. A fully polymerized grain of a defined size is introduced and a certain amount of organic phase is metered in (EP-PS 102 655; US-PS 154 184; FR-OS 2 238 717; FR-OS 2 238 718; DE-OS 2 338 133) . This method enables the grain size of the polymerization to be influenced via the metered amount.
Die Saatpolymerisation bedingt jedoch das Vorhandensein eines beschichtungsmittelfreien Saatkorns. Dessen Herstellung erfordert einen eigenen Polymerisationsprozeß und verringert damit die Raum/Zeit-Ausbeute. Die homogene Verteilung der nachdosierten organischen Phase bedingt eine sehr langsame Dosiergeschwindigkeit. Andernfalls kommt es zu einer unerwünschten Teilchenneubildung (Feingut).Seed polymerization, however, requires the presence of a seed grain free of coating agent. Its manufacture requires its own polymerization process and thus reduces the space / time yield. The homogeneous distribution of the replenished organic phase requires a very slow metering rate. Otherwise there is an undesirable formation of new particles (fines).
Aufgabe dieser Erfindung war es nun, ein Verfahren zur Körnungssteuerung der Suspensionspolymerisation zu finden, welches im kritischen Bereich stabil zu fahren ist und mit dem eine grobe Endkörnung erzielt werden kann.The object of this invention was to find a process for controlling the grain size of the suspension polymerization which can be driven stably in the critical area and with which a coarse final grain size can be achieved.
Überraschend gelöst wurde diese Aufgabe durch das erfindungsgemäße Verfahren, bei dem die Körnungsverteilung nicht mehr durch die Suspensionsmittelmenge gesteuert wird.
Vielmehr wird bis zum Absetzpunkt der Teilchen (70 % Styrolumsatz; ca. 180 min Reaktionszeit) eine feine und damit stabile Körnung eingestellt (hohes Suspensionsmittelniveau). Die Suspensionsrezeptur ist identisch mit der Standard-Rezeptur. Die Teilchenentwicklung verläuft bis zum Absetzpunkt relativ flach, das drastische Teilchenwachstum findet nicht statt. Ließe man diesen Ansatz nach Standard-Rezeptur weiter polymerisieren, würde man eine unerwünschte sehr feine Körnung erhalten. Die gewünschte Endkörnung wird dann durch Nachdosieren weiterer organischer Phase eingestellt. Die zufließende organische Phase diffundiert dabei in die bereits vorhandenen und stabilen Polymerteilchen. Dies führt zu einer kontinuierlichen Kornvergröberung. Eine Teilchenneubildung ist dabei unerwünscht, denn sie führt zu einer Erhöhung des Feinanteils. Die Dosiergeschwindigkeit sollte daher so gewählt werden, daß möglichst keine freien Styroltröpfchen in der Suspension vorhanden sind. Ein weiteres die Dosiergeschwindigkeit bestimmendes Kriterium ist der Absetzpunkt der Teilchen. Der Reststyrolgehalt sollte immer ≦ 30 Gew.-% sein. Auf diese Weise behalten die Teilchen ihre Identität und die Suspension kann nicht instabil werden.This object was surprisingly achieved by the process according to the invention, in which the particle size distribution is no longer controlled by the amount of suspension medium.
Rather, a fine and thus stable granulation is set up to the point of settling of the particles (70% styrene conversion; approx. 180 min reaction time) (high suspension medium level). The suspension recipe is identical to the standard recipe. The particle development is relatively flat up to the point of settling, the drastic particle growth does not take place. If this approach were to be polymerized further according to the standard recipe, an undesirable, very fine grain would be obtained. The desired final grain size is then adjusted by adding further organic phases. The incoming organic phase diffuses into the already existing and stable polymer particles. This leads to continuous grain coarsening. A new particle formation is undesirable because it leads to an increase in the fine fraction. The metering rate should therefore be chosen so that there are as far as possible no free styrene droplets in the suspension. Another criterion determining the dosing speed is the point of settling of the particles. The residual styrene content should always be ≦ 30% by weight. In this way, the particles retain their identity and the suspension cannot become unstable.
Nach Beendigung der Dosierung wird die Suspensionspolymerisation in herkömmlicher Weise fortgesetzt. Der normale Polymerisationszyklus wird praktisch nur für den Zeitraum der Dosierung unterbrochen. Die damit verbundene Zykluszeitverlängerung wird jedoch größtenteils durch die Erhöhung des Phasenverhältnisses org/wäßr. Phase und damit der Ausbeute kompensiert.After the metering has ended, the suspension polymerization is continued in a conventional manner. The normal polymerization cycle is practically interrupted only for the period of metering. The associated cycle time extension is largely due to the increase in the phase ratio org / aq. Phase and thus the yield is compensated.
In den Druckschriften US-PS 4 137 388, JP 62 053 306 und JP 5393/6 wurden zwar Nachdosierungen organischer Phasen vorgenommen. Diese Maßnahme diente jedoch nur der Verbesserung der Verarbeitungseigenschaften (Einfluß auf die Molmassenverteilung) oder der Verbesserung der optischen Eigenschaften.In the publications US Pat. No. 4,137,388, JP 62,053,306 and JP 5393/6, additional doses of organic phases were made. However, this measure only served to improve the processing properties (influence on the molar mass distribution) or to improve the optical properties.
Im Unterschied zu dem hier beschriebenen Verfahren erfolgt die Dosierung in den oben zitierten Schriften nicht mit einer bestimmten den Reststyrolgehalt konstant haltenden Dosiergeschwindigkeit und macht daher eine kontrollierte Körnungssteuerung unmöglich.In contrast to the method described here, the dosing in the documents cited above does not take place at a specific dosing rate that keeps the residual styrene content constant and therefore makes controlled grain control impossible.
Nach dem erfindungsgemäßen Verfahren werden 70 bis 90 %, vorzugsweise 80 bis 90 %, der zu polymerisierenden Menge an Styrol und ggf. Comonomere, in denen einer oder mehrere in Wasser unlösliche Initiatoren gelöst sind, unter Rühren in etwa derselben Menge Wasser dispergiert. Menge und Art der Polymerisationsinitiatoren werden mit der Polymerisationstemperatur so abgestimmt, daß der Endumsatz möglichst vollständig ist und die Molmasse des Polymeren die gewünschten Werte hat. Zur Stabilisierung der dispergierten Teilchen werden dem Reaktionsgemisch organische oder anorganische Dispergiermittel zugesetzt. Diese Mischung wird auf Polymerisationstemperatur (90 °C) aufgeheizt und anschließend bis zu einem 70%igen Styrolumsatz (ca. 180 min Reaktionszeit meist im Bereich von 120 bis 210 Minuten) polymerisiert. Danach wird das restliche Styrol (10 bis 30 % der Gesamtmenge), welches Initiator und Dispergiermittel enthält, dem Reaktionsgemisch innerhalb von 1 bis 3 Stunden, vorzugsweise 1 bis 2 Stunden, zudosiert.In the process according to the invention, 70 to 90%, preferably 80 to 90%, of the amount of styrene and, if appropriate, comonomers to be polymerized, in which one or more water-insoluble initiators are dissolved, dispersed in approximately the same amount of water with stirring. The amount and type of polymerization initiators are coordinated with the polymerization temperature so that the end conversion is as complete as possible and the molar mass of the polymer has the desired values. Organic or inorganic dispersants are added to the reaction mixture to stabilize the dispersed particles. This mixture is heated to the polymerization temperature (90 ° C.) and then polymerized to a 70% styrene conversion (about 180 min reaction time, usually in the range from 120 to 210 minutes). The remaining styrene (10 to 30% of the total amount), which contains initiator and dispersant, is then metered into the reaction mixture in the course of 1 to 3 hours, preferably 1 to 2 hours.
Die Dosiergeschwindigkeit sollte dabei derart gewählt werden, daß der Restmonomergehalt immer kleiner/gleich 30 Gew. % beträgt.The metering rate should be chosen such that the residual monomer content is always less than or equal to 30% by weight.
Im Anschluß an die Nachdosierung der organischen Phase wird der Ansatz auspolymerisiert.Following the metering in of the organic phase, the batch is polymerized out.
Als optimal im Hinblick auf die Zielgröße Kornvergröberung erwies sich eine 2stündige Dosierung von 20 Gew.-% organischer Phase nach 180 min Reaktionszeit.A 2-hour dosing of 20% by weight of organic phase after a reaction time of 180 minutes proved to be optimal with regard to the target size of grain coarsening.
Für die Herstellung der expandierbaren Styrolpolymerisate werden als Monomer Styrol oder Monomergemische mit mindestens 50 Gewichtsprozent Styrol eingesetzt. Geeignete Comonomere sind z. B. α-Methylstyrol, kernhalogenierte Styrole, Acrylnitril, Ester der Acryl- und Methacrylsäure von Alkoholen mit 1 bis 8 Kohlenstoffatomen, N-Vinylverbindungen, wie N-Vinylcarbazol.For the production of the expandable styrene polymers, styrene or monomer mixtures with at least 50 percent by weight of styrene are used as the monomer. Suitable comonomers are e.g. B. α-methyl styrene, halogenated styrenes, acrylonitrile, esters of acrylic and methacrylic acid of alcohols with 1 to 8 carbon atoms, N-vinyl compounds, such as N-vinyl carbazole.
Die Suspensionspolymerisation wird bei Temperaturen von 80 bis 130 °C durchgeführt. Sie wird in üblicher Weise mit einer oder mehreren radikalbildenden Substanzen initiiert, wobei t-Butylbenzoat, t-Butylperoctoat, Di-t-butylperoxid, Dibenzoylperoxid oder deren Mischungen als Beispiele genannt seien.The suspension polymerization is carried out at temperatures from 80 to 130 ° C. It is initiated in the usual way with one or more radical-forming substances, examples being t-butyl benzoate, t-butyl peroctoate, di-t-butyl peroxide, dibenzoyl peroxide or mixtures thereof.
Als Suspensionsstabilisatoren können in bekannter Weise organische Schutzkolloide, wie Polyvinylalkohol, Polyvinylpyrrolidon, Polyvinylpyrrolidoncopolymerisate und Hydroxyalkylcellulosen oder mineralische Suspendierhilfsmittel, wie fein verteiltes Tricaliumphosphat und Bariumphosphat oder auch Gemische aus organischen Schutzkolloiden und mineralischen Suspendiermittel verwendet werden.In a known manner, organic protective colloids such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl pyrrolidone copolymers and hydroxyalkyl celluloses or mineral suspension aids such as finely divided tricalium phosphate and barium phosphate or else mixtures of organic protective colloids and mineral suspending agents can be used as suspension stabilizers.
Das Treibmittel für die Polymerperlen kann je nach Verfahren entweder während oder nach der Polymerisation zugegeben werden. Vor Beendigung der Nachdosierung ist eine Treibmittelzugabe jedoch nicht möglich.The blowing agent for the polymer beads can be added either during or after the polymerization, depending on the process. It is not possible to add propellant before the end of the dosing.
Als Treibmittel werden die bekannten niedrigsiedenden, nur quellenden, flüssigen Kohlenwasserstoffe, wie Pentan, Hexan, cycloaliphatische Kohlenwasserstoffe, wie Cyclohexan oder Halogenkohlenwasserstoffe, wie Dichlordifluormethan, 1,2,2-Trifluor-1,1,2-trichlorethan oder auch Mischungen dieser Verbindungen verwendet. Die Menge an Treib mittel liegt bei 3 bis 15 Gew.-%, vorzugsweise zwischen 5 und 8 Gew.-% bezogen auf das Styrolpolymerisat.The known low-boiling, only swelling, liquid hydrocarbons, such as pentane, hexane, cycloaliphatic hydrocarbons, such as cyclohexane or halogenated hydrocarbons, such as dichlorodifluoromethane, 1,2,2-trifluoro-1,1,2-trichloroethane or else mixtures of these compounds, are used as blowing agents . The amount of blowing agent is 3 to 15 wt .-%, preferably between 5 and 8 wt .-% based on the styrene polymer.
Die expandierbaren Styrolpolymerisate können die üblichen Flammschutzmittel wie organische Halogenverbindungen, insbesondere Bromverbindungen, enthalten; insbesondere seien genannt die vollständig oder partiell bromierten Oligomeren des Butadiens oder des Isoprens mit einem mittleren Polymerisationsgrad von 2 bis 20, z. B. 1,2,5,6-Tetrabromcyclooctan, 1,2,5,6,9,10-Hexabromcyclodecan, bromiertes Polybutadien mit einem Polymerisationsgrad von z. B. 3 bis 15.The expandable styrene polymers can contain the usual flame retardants such as organic halogen compounds, especially bromine compounds; the fully or partially brominated oligomers of butadiene or isoprene with an average degree of polymerization of 2 to 20, e.g. B. 1,2,5,6-tetrabromocyclooctane, 1,2,5,6,9,10-hexabromocyclodecane, brominated polybutadiene with a degree of polymerization of e.g. B. 3 to 15.
Die organischen Halogenverbindungen sind in Mengen von 0,4 bis 3 Gew.-% im expandierbaren Styrolpolymerisat enthalten. Zusätzlich zu den flammhemmenden Halogenverbindungen können die bekannten Synergisten in üblichen Mengen eingesetzt werden, vorzugsweise organische Peroxide, insbesondere solche mit einer Halbwertszeit von mindestens zwei Stunden bei 373 K.The organic halogen compounds are present in the expandable styrene polymer in amounts of 0.4 to 3% by weight. In addition to the flame-retardant halogen compounds, the known synergists can be used in customary amounts, preferably organic peroxides, especially those with a half-life of at least two hours at 373 K.
Falls gewünscht, können die Halogenverbindungen auch in bekannter Weise in Mengen von 0,05 bis 1 Gew.-% zur Verbesserung der Mindestverweilzeit eingesetzt werden.If desired, the halogen compounds can also be used in a known manner in amounts of 0.05 to 1% by weight to improve the minimum residence time be used.
Die expandierbaren Styrolpolymerisate können außerdem Zuschlagstoffe wie Farbstoffe, Füllstoffe und Stabilisierungsmittel enthalten. Sie liegen nach der Herstellung in Perlform vor und haben einen Teilchendurchmesser zwischen 0,5 und 2,0 mm.The expandable styrene polymers can also contain additives such as dyes, fillers and stabilizers. After production they are in pearl form and have a particle diameter between 0.5 and 2.0 mm.
Die Styrolpolymerisate werden nach den üblichen Verfahren in vorgeschäumtem Zustand durch Erhitzen in Formen, welche nicht gasdicht schließen, weiter aufgeschäumt und zu Schaumstoffkörpern versintert, die in ihren Ausmaßen dem Innenhohlraum der verwendeten Formen entsprechen.The styrene polymers are foamed further in the pre-expanded state by heating in molds which do not close in a gas-tight manner and sintered to form foam bodies which correspond in their dimensions to the internal cavity of the molds used.
In einem 150-1-Reaktor werden 50 kg Wasser mit 76,4 g Hydroxyethlcellulose, 191 g Tricalciumphosphat und 5,1 g EDTA als Suspensionsmedium vorgelegt. Dazu werden 50 kg Styrol, die 203,6 g Benzoylperoxid und 127,3 g Tertiärbutylperbenzoat enthalten, gegeben.50 kg of water with 76.4 g of hydroxyethyl cellulose, 191 g of tricalcium phosphate and 5.1 g of EDTA as the suspension medium are placed in a 150 l reactor. 50 kg of styrene, which contain 203.6 g of benzoyl peroxide and 127.3 g of tertiary butyl perbenzoate, are added.
Die Mischung wird unter Rühren auf 90 °C aufgeheizt und 3 h bei dieser Temperatur gehalten. Danach werden innerhalb 2 h weitere 10,2 kg Styrol, die 40,8 g Benzoylperoxid und 25,5 g Tertiärbutylperbenzoat enthalten, zudosiert. Nach Beendigung der Dosierung wird mit 25,5 g Polyvinylalkohol nachstabilisiert.The mixture is heated to 90 ° C. with stirring and kept at this temperature for 3 h. A further 10.2 kg of styrene, which contain 40.8 g of benzoyl peroxide and 25.5 g of tertiary butyl perbenzoate, are then metered in within 2 hours. After metering is complete, the mixture is stabilized with 25.5 g of polyvinyl alcohol.
Anschließend werden insgesamt 3,7kg Pentan innerhalb 1 h unter gleichzeitigem Aufheizen auf 110 °C zugegeben. Nach weiteren 5 h Polymerisationszeit wird die Suspension ausgefahren, das Polymerisat abfiltriert, getrocknet und gesiebt.
- Ausbeute:
- 65,0 kg
- K-Wert:
- 56,8
- mono-Styrol:
- 0,12 Gew.-%
- Treibmittelgehalt:
- 6,68 Gew.-%
- Wassergehalt :
- 0,08 Gew.-%
- Feingut:
- 0,5 %
- Yield:
- 65.0 kg
- K value:
- 56.8
- mono-styrene:
- 0.12% by weight
- Blowing agent content:
- 6.68% by weight
- Water content:
- 0.08% by weight
- Fine goods:
- 0.5%
Reaktionsbedingungen und Reaktionstemperaturen wie Beispiel 1, jedoch 0,1 % Polyvinylalkohol anstelle der Hydroxyethylcellulose und des Tricalciumphosphats.
- Ausbeute:
- 65,0 kg
- K-Wert:
- 56,3
- mono-Styrol:
- 0,10 Gew.-%
- Treibmittelgehalt:
- 6,42 Gew.-%
- Wassergehalt :
- 0,24 Gew.-%
- Feingut:
- 0,2%
- Yield:
- 65.0 kg
- K value:
- 56.3
- mono-styrene:
- 0.10% by weight
- Blowing agent content:
- 6.42% by weight
- Water content:
- 0.24% by weight
- Fine goods:
- 0.2%
Reaktionsbedingungen und Reaktionstemperaturen wie Beispiel 1, jedoch ohne Nachdosierung eines Teils der organischen Phase.
- Ausbeute:
- 55 kg
- K-Wert:
- 54,0
- mono-Styrol:
- 0,29 Gew.-%
- Treibmittelgehalt:
- 6,16 Gew.-%
- Wassergehalt:
- 0,11 Gew.-%
- Feingut:
- 2,9%
- Yield:
- 55 kg
- K value:
- 54.0
- mono-styrene:
- 0.29% by weight
- Blowing agent content:
- 6.16% by weight
- Water content:
- 0.11% by weight
- Fine goods:
- 2.9%
Claims (4)
dadurch gekennzeichnet,
daß mindestens 70 % der Monomeren, bezogen auf das Gesamtmonomer, in wäßriger Suspension in Gegenwart von Dispergiermittel, Initiator und sonstigen Zuschlagstoffen zunächst bis zu einem Umsatz von wenigstens 70 Gew.-% polymerisiert werden und dann die restliche Menge Monomer, Initiator und ggf. weitere Zuschlagsstoffe innerhalb von einer bis zu drei Stunden nachdosiert werden.Process for the preparation of expandable styrene polymers by polymerizing styrene and, if appropriate, customary comonomers in aqueous suspension with stirring in the presence of monomer-soluble, radical-forming initiators and dispersants,
characterized,
that at least 70% of the monomers, based on the total monomer, are first polymerized in aqueous suspension in the presence of dispersant, initiator and other additives up to a conversion of at least 70% by weight and then the remaining amount of monomer, initiator and, if appropriate, others Additives can be added within one to three hours.
dadurch gekennzeichnet,
daß das vorgelegte Monomer 120 bis 210 Minuten (bis zum Absetzpunkt) polymerisiert und anschließend das restliche Monomer zudosiert wird.Method according to claim 1,
characterized,
that the monomer initially polymerized for 120 to 210 minutes (to the point of settling) and then the remaining monomer is metered in.
dadurch gekennzeichnet,
daß die nachdosierte Monomermenge 10 bis 20 Gew.-%, bezogen auf das Gesamtmonomer, beträgt.Method according to claim 1,
characterized,
that the metered amount of monomer is 10 to 20 wt .-%, based on the total monomer.
dadurch gekennzeichnet,
daß die Dosiergeschwindigkeit derart gewählt wird, daß der Restmonomergehalt immer kleiner/gleich 30 Gew.-% beträgt.Method according to claim 1,
characterized,
that the metering rate is selected such that the residual monomer content is always less than / equal to 30% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4029298A DE4029298A1 (en) | 1990-09-15 | 1990-09-15 | PROCESS FOR CORE CONTROL IN THE MANUFACTURE OF EXPANDABLE STYRENE POLYMERISES BY SUSPENSION POLYMERIZATION |
| DE4029298 | 1990-09-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0476256A1 true EP0476256A1 (en) | 1992-03-25 |
| EP0476256B1 EP0476256B1 (en) | 1995-06-14 |
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ID=6414312
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91111717A Expired - Lifetime EP0476256B1 (en) | 1990-09-15 | 1991-07-13 | Process for controlling granulation in the preparation of expandable styrene polymers by suspension polymerization |
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| Country | Link |
|---|---|
| US (1) | US5189069A (en) |
| EP (1) | EP0476256B1 (en) |
| JP (1) | JPH04279607A (en) |
| KR (1) | KR0161984B1 (en) |
| CN (1) | CN1059912A (en) |
| BR (1) | BR9103948A (en) |
| CA (1) | CA2051324A1 (en) |
| DE (2) | DE4029298A1 (en) |
| ES (1) | ES2073075T3 (en) |
| FI (1) | FI914278A (en) |
| MX (1) | MX174341B (en) |
| NO (1) | NO913632L (en) |
| TW (1) | TW210345B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007144273A1 (en) * | 2006-06-13 | 2007-12-21 | Basf Se | Process for production of expandable styrene polymers |
| WO2011069983A1 (en) * | 2009-12-10 | 2011-06-16 | Akzo Nobel Chemicals International B.V. | Process for the polymerization of styrene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980059280A (en) * | 1996-12-31 | 1998-10-07 | 박영구 | Method for preparing sorbic acid |
| KR19980059281A (en) * | 1996-12-31 | 1998-10-07 | 박영구 | Method for preparing sorbic acid |
| GB9721603D0 (en) | 1997-10-10 | 1997-12-10 | Dyno Ind Asa | Method |
| DE19816464C1 (en) * | 1998-04-14 | 1999-12-09 | Buna Sow Leuna Olefinverb Gmbh | Preparation of expanded polystyrene with narrow core size distribution |
| DE19816461C1 (en) * | 1998-04-14 | 1999-12-09 | Buna Sow Leuna Olefinverb Gmbh | Preparation of expanded polystyrene with narrow core size distribution |
| DE19816469C1 (en) * | 1998-04-14 | 1999-12-09 | Buna Sow Leuna Olefinverb Gmbh | Preparation of expanded polystyrene with narrow core size distribution |
| AU3819399A (en) * | 1998-04-17 | 1999-11-08 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of expandable polymer particles |
| KR100280216B1 (en) * | 1998-06-25 | 2001-02-01 | 황규억 | Method for preparing expandable styrene terpolymer copolymer beads |
| US6360807B2 (en) * | 1999-12-29 | 2002-03-26 | Styrochem Delaware, Inc. | Processes for forming styrenic copolymers |
| US6991763B2 (en) * | 2000-04-26 | 2006-01-31 | Rohm And Haas Company | Polymer process |
| KR100544780B1 (en) * | 2002-08-19 | 2006-01-23 | 주식회사 효성 | Antibacterial sea-island polyester composite filament and precipitation thereof |
| KR100488622B1 (en) * | 2002-10-10 | 2005-05-11 | 주식회사 효성 | Process for the preparation of splittable composite fibers having antimicrobial and deodorant properties |
| KR100481358B1 (en) * | 2002-11-25 | 2005-04-07 | 주식회사 효성 | A multifunctional polyester fiber and its manufacturing process |
| PL1613672T3 (en) * | 2003-04-14 | 2019-12-31 | Nouryon Chemicals International B.V. | Dosing of peroxide to a suspension process wherein styrene is polymerized |
| JP5214923B2 (en) * | 2007-07-27 | 2013-06-19 | 株式会社ジェイエスピー | Method for producing vinyl resin particles |
| US8455559B2 (en) * | 2010-03-12 | 2013-06-04 | Basf Se | Preparing expandable styrene polymers |
| JP5721337B2 (en) * | 2010-03-23 | 2015-05-20 | 積水化成品工業株式会社 | A method for producing expandable polystyrene resin particles, a method for producing pre-expanded polystyrene resin particles, and a method for producing a polystyrene resin foam molded article. |
| MX2014006977A (en) * | 2011-12-21 | 2014-08-26 | Basf Se | Method for producing expandable styrene polymers containing particulate additives. |
| US9453083B2 (en) | 2013-03-14 | 2016-09-27 | Saudi Basic Industries Corporation | Vinyl polymers prepared via suspension polymerization and methods thereof |
| JP6672166B2 (en) * | 2013-12-30 | 2020-03-25 | アベリス アーエス | Method for preparing solid particulate vinyl aromatic polymer composition for preparation |
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|---|---|---|---|---|
| US4363881A (en) * | 1980-11-26 | 1982-12-14 | Cellofoam A.G. | Method of making uniformly-sized expandable polymeric particles |
| US4582859A (en) * | 1983-12-02 | 1986-04-15 | Rohm And Haas Company | Process for producing an expanded seed copolymer and product therefrom |
| US4731388A (en) * | 1986-01-23 | 1988-03-15 | Mitsubishi Yuka Badische Co., Ltd. | Process for producing expandable styrene-based polymer beads |
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| FR1370635A (en) * | 1963-05-20 | 1964-08-28 | Pechiney Saint Gobain | Process for the production of expandable styrene copolymers |
| SE346114B (en) * | 1965-05-13 | 1972-06-26 | Hoechst Ag | |
| GB1344060A (en) * | 1970-06-19 | 1974-01-16 | Bp Chem Int Ltd | Polymerisation of vinyl aromatic monomers |
| US3928261A (en) * | 1973-05-17 | 1975-12-23 | Minnesota Mining & Mfg | Water removable film-forming compositions for topical application to skin |
| US4174425A (en) * | 1973-07-23 | 1979-11-13 | Sekisui Kasehin Kogyo Kabushiki Kaisha | Process of preparing styrenic polymer foams |
| SE7702990L (en) * | 1976-03-19 | 1977-09-20 | Minnesota Mining & Mfg | TROPICAL ADMINISTRATIVE SYSTEM FOR MEDICINAL PRODUCTS WITH INCREASED PEUTRATION |
| US4137388A (en) * | 1978-01-06 | 1979-01-30 | United States Steel Corporation | Polystyrene with distinct moieties of molecular weight distribution |
| IT1198338B (en) * | 1980-07-02 | 1988-12-21 | Montedison Spa | PROCESS FOR PRODUCING COPOLYMERS OF VINYL-AROMATIC MONOMERS WITH ETHYLENICALLY UNSATURATED NITRILS |
| LU83949A1 (en) * | 1982-02-16 | 1983-09-02 | Oreal | COMPOSITION FOR THE TREATMENT OF KERATINIC MATERIALS CONTAINING AT LEAST ONE CATIONIC POLYMER AND AT LEAST ONE ANIONIC LATEX |
| US4489058A (en) * | 1983-05-23 | 1984-12-18 | The Dow Chemical Company | Acne control method |
| JPS6263508A (en) * | 1985-09-13 | 1987-03-20 | Kao Corp | Hair cosmetic |
| JPH0253306A (en) * | 1988-08-18 | 1990-02-22 | Sony Corp | Mixer circuit |
-
1990
- 1990-09-15 DE DE4029298A patent/DE4029298A1/en not_active Withdrawn
-
1991
- 1991-06-28 TW TW080105018A patent/TW210345B/zh active
- 1991-07-05 US US07/726,288 patent/US5189069A/en not_active Expired - Fee Related
- 1991-07-13 EP EP91111717A patent/EP0476256B1/en not_active Expired - Lifetime
- 1991-07-13 DE DE59105698T patent/DE59105698D1/en not_active Expired - Fee Related
- 1991-07-13 ES ES91111717T patent/ES2073075T3/en not_active Expired - Lifetime
- 1991-07-16 MX MX9100232A patent/MX174341B/en not_active IP Right Cessation
- 1991-09-11 FI FI914278A patent/FI914278A/en not_active Application Discontinuation
- 1991-09-13 BR BR919103948A patent/BR9103948A/en unknown
- 1991-09-13 JP JP3235002A patent/JPH04279607A/en active Pending
- 1991-09-13 KR KR1019910015961A patent/KR0161984B1/en not_active IP Right Cessation
- 1991-09-13 CA CA002051324A patent/CA2051324A1/en not_active Abandoned
- 1991-09-13 NO NO91913632A patent/NO913632L/en unknown
- 1991-09-14 CN CN91108947A patent/CN1059912A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4363881A (en) * | 1980-11-26 | 1982-12-14 | Cellofoam A.G. | Method of making uniformly-sized expandable polymeric particles |
| US4582859A (en) * | 1983-12-02 | 1986-04-15 | Rohm And Haas Company | Process for producing an expanded seed copolymer and product therefrom |
| US4731388A (en) * | 1986-01-23 | 1988-03-15 | Mitsubishi Yuka Badische Co., Ltd. | Process for producing expandable styrene-based polymer beads |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007144273A1 (en) * | 2006-06-13 | 2007-12-21 | Basf Se | Process for production of expandable styrene polymers |
| WO2011069983A1 (en) * | 2009-12-10 | 2011-06-16 | Akzo Nobel Chemicals International B.V. | Process for the polymerization of styrene |
| AU2010329986B2 (en) * | 2009-12-10 | 2014-12-04 | Akzo Nobel Chemicals International B.V. | Process for the polymerization of styrene |
Also Published As
| Publication number | Publication date |
|---|---|
| MX174341B (en) | 1994-05-09 |
| US5189069A (en) | 1993-02-23 |
| BR9103948A (en) | 1992-05-26 |
| DE4029298A1 (en) | 1992-03-19 |
| JPH04279607A (en) | 1992-10-05 |
| KR920006382A (en) | 1992-04-27 |
| CN1059912A (en) | 1992-04-01 |
| ES2073075T3 (en) | 1995-08-01 |
| FI914278A (en) | 1992-03-16 |
| KR0161984B1 (en) | 1999-01-15 |
| TW210345B (en) | 1993-08-01 |
| FI914278A0 (en) | 1991-09-11 |
| DE59105698D1 (en) | 1995-07-20 |
| NO913632L (en) | 1992-03-16 |
| NO913632D0 (en) | 1991-09-13 |
| EP0476256B1 (en) | 1995-06-14 |
| CA2051324A1 (en) | 1992-03-16 |
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